TADDOL and titanium ( ) taddolate dendrimers and composition

ABSTRACT

TADDOL dendrimers are described. Their use as crosslinkers in polymerisation reactions and the use of Ti salts of polymer-bound TADDOL dendrimers as catalysts in enantioselective addition reactions is disclosed.

This application is a divisional of application Ser. No. 08/959,390,Oct. 28, 1997, U.S. Pat. No. 6,211,316.

This invention relates to dendrimers of TADDOLs, in particulardendrimers of α,α,α′,α′-tetraaryl-1,2-dioxolane-dimethanol, titanium(IV) salts thereof and the use of polymer-bound dendrimer Ti-saltsthereof in syntheses involving carbon-carbon bond formation, inparticular the catalytic addition of diethylzinc to aldelydes.

It is known to incorporate TADDOL into a crosslinked (divinylbenzene)polystyrene polymer and use the corresponding titanate in additionreactions of diethyl zinc to aldelydes. The known polymer-bound TADDOLsare characterised in that the TADDOL moiety depends from the polystyrenechain through the dioxolane group of said TADDOL.

The polymer-bound TADDOLs are heterogeneous catalysts and are thereforemore easily removed from a reaction mixture than a free TADDOL which ishomogeneous with a reaction mixture. However, known polymer-boundtitanium salts of TADDOLs are less effective than said free titaniumsalts of TADDOLs at catalysing the aforementioned reactions. Thereremains a need to provide a polymer-bound TADDOL, the TADDOLate of whichis more reactive than the known polymer-bound TADDOLates.

Surprisingly it has now been found that a dendrimer TADDOLate bound to apolymer is more active as a catalyst in carbon-carbon bond-formingreactions, in particular in the catalytic reaction of diethylzinc toaldehydes, than the known polymer-bound TADDOlates.

Accordingly, the invention provides in one of its aspects a dendrimerTADDOL.

TADDOLs and the syntheses for forming same are known in the art see, forexample Helvetica Chim. Acta, 77, 2071-2110, (1994) which isincorporated herein by reference. TADDOLs of the present invention maybe any of those known in the art, in particular 2-mono- or2,2-disubstituted at the 1,3-dioxolane group. Substituents at the2-position may be optionally substituted alkyl, e.g. methyl or ethyl,and optionally substituted phenyl or naphthyl. Said substituents may besubstituted with, for example halogen, e.g. Cl Br or F, OH or alkoxy.When the 1,3-dioxolane group is 2,2-disubstituted it is preferably2,2-dialkyl substituted, more particularly 2,2-dimethyl substituted.

The aryl groups of the preferred TADDOLs may be phenyl, substitutedphenyl, naphthyl or substituted naphthyl. Insofar as the aryl groups aresubstituted, they may be identically or differently substituted.

Dendrimers are known in the art, see for example D. A. Tomalia et. al.Angew. Chem. (1990), 102, 119 and N. Ardoin et. al. Bull. Soc. Chem. Fr.1995, 132, 875-909 which are incorporated herein by reference. Bydendrimer of TADDOL or TADDOLate is meant a macromolecule comprising acentral core formed by the aforementioned TADDOL or TADDOLate moiety anddepending radially from said core (ususally branched) substituents.

There are many types of dendritic substituents known in the art (see theaforementioned references). Any of the known dendritic substituents maybe employed as substituents in the present invention provided that theyare unreactive with respect to the reagents used in the catalyticsyntheses or do not otherwise interfere with the catalytic effect of theTADDOlate core, for example by sterically crowding the TADDOLate core.

Dendritic substituents may be characterised by their degree ofbranching. A dendritic substituent may, in fact, not have any branchpoints in which case it is referred to as a zero (0) generationsubstituent. More typically however, dendritic substituents have one(first generation), two (second generation) or more branch points, forexample up to 10 branch points. Preferred dendritic substituents are oneto three generation number substituents, more particularly two or threegeneration number substituents.

As examples of dendritic substituents there may be mentioned those basedon branched hydrocarbon chains, i.e. alkyl or aryl chains, polyethers,e.g. alkyl ethers, aryl ethers or arylalkyl ethers, thio ethers orpolyamides. Most preferred dendritic substituents are based ondihydroxybenzylbromide, in particular 3,5-dihydroxybenzylbromide, thebranched substituent thereby being created using an iterative syntheticprocess of reacting said benzyl bromide moiety of one molecule with thehydroxy substituents of another molecule until a substituent of thedesired generation number is obtained.

Dendrimers according to the invention may bear terminal functionalgroups which can react with appropriate functionality of a polymer (or amonomer unit thereof) in order to bind said dendrimer to a polymersupport.

Preferably said functionality is an unsaturated group, more preferablyan alkene group, e.g. vinyl group or a styryl group. The terminalfunctional groups may be connected to the dendrimer chain according toknown processes, for example as an end-capping step as part of theiterative process discussed above.

Preferred dendrimer TADDOLs have only one dendritic substituent attachedto each aryl group, the dendritic substituents may be connected to thearyl groups by a carbon-carbon bond or a carbon-heteroatom bond, e.g.carbon-oxygen, carbon-nitrogen or carbon-sulphur bond. Preferably thedendritic substituents are attached to the aryl groups through acarbon-oxygen bond.

Dendritic substituents useful in the invention may be made according tosyntheses known in the art (see the aforementioned references which areincorporated herein by reference).

The invention provides in another of its aspects a dendrimer ofα,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanolate of titanium (IV)hereinafter referred to as a dendrimer TADDOLate.

The source of titanium (IV) may be any of the known alkyl, aryl oralkoxy titanium complexes known in the art. A preferred source oftitanium (IV) are tetra alkoxy titanates, more particularlytetraisopropyloxy titanate. TADDOLates may be 1:1 complexes, that is oneTADDOL ligand complexed to one titanium atom, or a 2:1 complex whereintwo TADDOL ligands are complexed with one titanium atom. 1:1 TADDOLatesare preferred. A more preferred titanium TADDOLate is thediisopropoxy-Ti-TADDOLate.

The insertion of the Ti atom into the TADDOL core may be carried outaccording to known syntheses. Preferred reaction conditions for forminga TADDOL-titanate are described in Tetrahedron 50 4363-4384 (1994) whichis incorporated herein by reference.

A more preferred dendrimer TADDOLate has dendritic substituents based ondihydroxybenzylbromide, in particular 3,5-dihydroxybenzylbromide. Morepreferably the TADDOLate is a 2- or 3-generation number dendrimer, inparticular, being terminally substituted with an unsaturated group, e.ga vinyl group or a styryl group. The most preferred dendrimer TADDOLateare the preferred dendrimers aforementioned with one dendriticsubstituent attached to each aryl group of the TADDOLate core.

In another aspect of the invention there is provided a polymercross-linked with a TADDOL or TADDOLate as hereinabove described.

Polymers according to the invention may be made up of any suitablemonomeric units at least some of which will react with the terminalunsaturated groups of the dendritically substituted TADDOLs orTADDOLates. The terminal unsaturation of the dendrimers may react withother said monomeric units in a copolymerisation reaction therebybecoming incorporated into the polymer chain. Alternatively, theterminal unsaturation may react with functionality depending from saidother monomeric units or a polymer formed from said monomeric unitsthereby forming chains depending from the polymer or copolymer backbone.However the terminal unsaturation reacts with the respective monomericunits or polymers formed therefrom, when two or more of the dendriticsubstituents bearing terminal unsaturated units of the dendrimer TADDOLinteract with the polymer the dendrimer essentially acts as acrosslinker for the polymer.

Preferably the unsaturated terminal groups of the dendrimer TADDOL takepart in a copolymerisation with styrene. The polymerisation reaction maybe carried out according to known synthetic methods. The amount ofdendrimer TADDOL employed relative to the amounts of styrene will dependupon the degree of crosslinking required in order to achieve the desiredphysical properties of the resultant polymer. Polymers with differingphysical properties may be obtained by routine experimentation.

In another aspect of the invention there is provided a polymer-bounddendrimer TADDOL or its TADDOLate of titanium (IV).

Polymer-bound dendrimers TADDOLs and TADDOLates of titanium (IV) may bein the form of particles, e.g. beads or granules. The particle size ofsaid beads or granules may be about 0.25 to 0.4 mm, more preferably 0.3mm.

The loading of a dendrimer TADDOLate of titanium (IV) on the polymer maybe in the range of about 0.5 to 1.0 mmol per gram of polymer, morepreferably 0.6 to 0.7 mmol, in particular 0.63 mmol per gram of polymer.

Whilst the dendrimer TADDOL ate of titanium may be formed prior tobinding to a polymer as described hereinabove it is preferred thatpolymer-bound dendrimer TADDOLs are converted to the correspondingpolymer-bound TADDOLate according to substantially the same syntheticprocedure used to convert non-polymer-bound TADDOLs to the correspondingTADDOLates.

Polymer-bound dendrimer TADDOLates may be formed by treating directbeads of polymer-bound TADDOL with, for example tetraisopropyloxytitanate in an organic solvent, e.g. toluene according to conventionalmethods.

A by-product of the reaction of the preferred titanium-containingreagent, isopropyl alcohol, may be azeotropically removed to give thetitanium loaded polymer beads.

In another aspect of the invention there is provided the use of apolymer-bound dendrimer TADDOLate of titanium (IV) as hereinabovedescribed (hereinafter referred to as pb-Ti-TADDOLate) in catalytic orstoichiometric synthetic transformations.

Said transformations may be any of those previously effected by usinghomogeneous TADDOLate catalysts or known polymer-bound TADDOLates, forexample additions to carbonyl compounds, Diels-Alder reactions anddesymmetrisation of meso compounds.

In particular, the pb-Ti-TADDOLate of the invention is useful in thecatalytic enantioselective nucleophilic addition to carbonyl compounds,more particularly the nucleophilic addition of dialkylzinc, e.g..diethyl zinc to carbonyl compounds, in particular aldehydes, e.g.benzaldehyde.

The catalysis of the reaction between diethyl zinc and benzaldehydeusing a pb-Ti-TADDOLate of the invention may be carried out under knownconditions for effecting metal mediated transformation of benzaldehydeusing diethyl zinc (See Helvetica Chim. Acta (1996) 79, 1710 which isincorporated herein by reference).

pb-Ti-TADDOLate, when used catalytically in the aforementioned synthetictransformations, e.g. the reaction of diethylzinc with benzaldehyde maybe present in amounts of up to 0.2 equivalent based on an equivalent ofeither one of the reactants.

The nucleophilic addition of diethylzinc to carbonyl compounds, e.g.addition of diethylzinc to benzaldehyde proceeds with yields andenantioselectivity which is comparable to reactions using homogenousTi-TADDOLate catalysis known in the art.

In the particular reaction of diethylzinc with benzaldehyde yields areobtained of up to 98% with enantioselectivity in the order of an er.(S:R) of 98:2.

Surprisingly we have found that the enantioselectivity decreases withincreased TADDOLate content in the polymer-bound dendrimers. A preferredpolymer-bound dendrimer is a first generation number dendrimer formedfrom copolymerisation of styrene:dendrimer TADDOL or TADDOLate in a moleratio of 20:1.

Further we have surprisingly found that activity of the pb-Ti-TADDOLatediffers according to the generation number of the polymer, thus forexample, 2nd generation number pb-Ti-TADDOLate may not be more effectivethan 1st generation number pb-Ti-TADDOLate and 3rd generation numbersand higher may be increasingly less active. In a preferred embodiment ofthe invention the denrimers are first generation number dendrimers.

Reaction times of syntheses using pb-Ti-TADDOLate according to theinvention, whilst being slower when compared to homogenous catalysiswith the corresponding TADDOLate, nevertheless are substantially fasterthan conventional polymer-bound TADDOLate catalysed reactions.

pb-Ti-TADDOLate, however, possess advantages over homogenous catalysis,for example ease of separation from the reactant (consequently they areeasily re-usable and potentially toxic and expensive materials can beisolated from the reaction mixture). Furthermore, the pb-Ti-TADDOLatecan be used many times, e.g. as much as 20 times, e.g 10 to 15 timeswithout significantly affecting yield or enantioselectivity.

A potential problem associated with using polymer-bound catalysts isthat the catalyst, usually formed as polymer beads or granules, tend tobe physically degraded as a result of abrasion from constant agitationof the reaction mixture. The polymer eventually may be reduced to a finepowder which may no longer be easily removed from the reaction mixture.

Surprisingly we have now found that if the polymer beads or granules maybe contained within a mesh within a reaction vessel the aforementionedphysical degradation of the polymer beads is essentially prevented.

Furthermore, despite the fact that the mesh contains the polymer-boundcatalyst within a relatively small area of the reaction vessel,nevertheless, there would appear to be sufficient reaction circulationthrough the mesh in contact with the polymer-bound catalyst that yields,reaction time, and enantioselectivity are not substantially affectedcompared with the non-constrained polymer-bound catalyst.

The mesh may be in the shape of a “tea bag” wherein two essentiallydisc-shaped meshes are arranged such that they sandwich the polymerbeads or granules and thereafter the edges of the disc-shaped meshes aresealed to form a pouch containing the polymer beads or granules.

The mesh may be formed of any suitable inert material, for examplepolypropylene. The mesh size may be sufficiently small to preventpolymer beads or granules from passing through the mesh and will dependupon the size of the polymer beads or granules. Typically the mesh sizemay be 0.3 to 0.05 mm, e.g. 0.1 mm.

The mesh may be fixed so as to be immobilised within a reaction vessel.Suitable fixing means may be provided by sandwiching the mesh betweentwo grills, e.g. glass grills which abut the inner wall of a reactionvessel.

There now follows a series of examples which serve to illustrate theinvention.

EXAMPLE 1 Syntheses

1. Preparation of the TADDOL (4R,5R)-2,2-Dimethyl-α,α,α′,α′-tetra(p-hydroxyphenyl)-1,3-dioxolan-4,5-dimethanol(1).

A 1L flask under an atmosphere of Argon is charged with a solution of83.5 g (0.48 mol) p-bromophenol in THF (600 ml). To this solution isadded with stirring 49.3 g (0.72 mol, 1.5 eq) of imidazole. Theresultant solution is cooled with an ice bath before adding 80.0 g(0.053 mol, 1.1 eq.) of TBDMSCl.

After addition, the mixture is allowed to warm to room temperaturewhereupon the mixture is left to stir for 20 hours.

Thereafter, diethylether (800 ml) and water (200 ml) is added to themixture and the organic phase is extracted, washed with water (3×500 ml)and dried over Mg SO₄ to yield a yellow oil. The yellow oil is distilledunder vacuum 129° C., 0.2 torr.) to yield 139 g (97.2% of a clear oil(TBDMS-protected phenol 1A).

In a 1L flask under Argon is placed 6.1 g (244 mmol, 5 eq.) of magnesiumturnings and a single iodine crystal. 70.0 g (244 mmol, 5 eq) 1A in THF(70 ml) is added slowly to the flask over a thirty minute period. Theresultant brown solution is stirred for a further 1 hour. Thereafter,12.0 g (48.7 mmol) of (4R,5R)-2,2-dimethyl-1,3-dioxolane-4,5-dicarboxylicethylester in THF (70 ml)is slowly added to the solution. The resultant mixture is stirred for 3hours whereupon a brown suspension is formed. The crude reaction mixtureis worked-up by adding 240 ml NH₄Cl and 350 ml water (both cooled bymeans of an ice bath) and diethylether (750 ml). The organic phase iscollected and the aqueous phase is washed with diethyl ether (3×500 ml).The organic phases are collected and combined and washed with NaClsolution (2×500 ml). Thereafter the organic phase is dried over MgSO₄and evaporated to dryness to yield a brown oil (56.5 g). To this oil isadded diethylether (150 ml) and methanol (200 ml) as a recrystallisingsolvent. The crude product is left to recrystallise over night whereupon30.5 g (63%) of white crystals of (4R,5R)-2,2-dimethyl-α,α,α′,α′-tetra(4tert-butyldimethylsiloxyphenyl)-1,3-dioxolane-4,5-dimethanol(1B) are obtained.

A 1L flask is charged with 16.3 (16.5 mmol) of (1B) in THF (310 ml)under an atmosphere of Argon. The solution is cooled to 0° C. with anice bath and 20.8 g (66 mmol, 4 eq) of TBAF is added. The resultantmixture is allowed to warm to room temperature and is thereafter stirredfor a further 48 hours whereupon a dark red reaction mixture isobtained. To the reaction mixture is added water (300 ml) anddiethylether (3×500 ml) and the organic phases are collected andcombined, dried over MgSO₄ and evaporated to dryness to yield an orangesolution (8.5 g, 97%) from which light-orange coloured crystalsprecipitate. The crude product was dissolved in adichloromethane/methanol mixture (10:1) and filtered through kieselgel.The solution was left to crystallise. A fine orange powder was obtained(6.5 g, 82.2%) of (1).

2. Synthesis of first-generation number dendritic substituent-3,5Di(4-vinyl benzyloxy) benzylbromide (2)

A 2L flask is charged with 37.8 g (224.6 mmol) of 3,5-dihydroxy benzoatein acetone (900 ml) under an Argon atmosphere. To this solution is added80 g (471.8 mmol, 2.1 eq) of 4-vinylbenzyl chloride. Thereafter, 11.7 g(45 mmol, 0.2 eq) of 18-C-6 and 65.2 g (655 mmol, 2.2 eq) of K₂CO₃ isadded. The resultant yellow mixture is stirred gently at 60° C. for 40hours. Thereafter, the solution is filtered to provide a brownishfiltrate and a yellowish filtercake. Diethylether (800 ml) and water(500 ml) are added to the solution and the organic phase collected. Thewater phase is further extracted with diethylether (500 ml) andmethylene chloride (500 ml). The organic phases are collected, andcombined, dried over MgSO₄ and evaporated to dryness. A brown-orange oilis obtained and suspended therein, some white particulate matter. Theoil is dissolved in acetone and hexane is added to effectrecrystallisation. White crystals are formed (76.9 g, 85.5%) of3,5-di(4-vinylbenzyloxy) benzoate (2A).

A 1L flask is charged with 10.0 g (268.6 mmol, 2.3 eq) of LiAlH₄ in THF(250 ml) under an argon atmosphere. The resultant solution is cooledwith an ice bath and 46.9 g (116.9 mmol) of ester (2A) in THF (250 ml)is added dropwise with stirring and the mixture, stirred over a 2 hourperiod. Thereafter water (10 ml) and 15% NaOH (10 ml) and finally water(24 ml) is added to the mixture. The grey precipitate is filtered andthe filtrate is washed with diethylether. Thereafter water (500 ml) isadded and the organic phase is collected. The remaining aqueous phase isfurther extracted with diethylether (3×500 ml) and the organic phasesare collected and combined, dried over MgSO₄ and evaporated to dryness.A colourless oil is obtained (38.7 g, 88.5%). Addition of a littlehexane effects precipitation of white crystals of3,5-di(4-vinylbenzyloxy) benzylalcohol (2B).

A 1L flask is charged with 64.5 g (173 mmol) of (2B) in THF (250 ml)under an argon atmosphere. Thereafter, 68.1 g (260 mmol, 1.5 eq) of PPh₃and then 86.2 g (260 mmol, 1.5 eq) of CBr₄ are added and the resultantmixture stirred gently for 1 hour in an ice bath whereupon a milkysuspension is obtained. To this suspension is added water (600 ml) anddiethylether (400 ml). The organic phase is collected and the aqueousphase is further extracted with diethylether (2×500 ml). The organicphases are collected and combined, dried over MgSO₄ and evaporated todryness. A yellow oil is obtained which is dissolved in hexane/acetone9:1 and filtered over Kieselgel. The resultant solution is left torecrystallise to yield fine white crystals of3,5-di(4-vinylbenzyloxy)benzylbromide (2).

3. Synthesis of a second generation number dendritic substituent

3,5-di(3,5-di(4-vinylbenzyloxy)benzyloxy)benzylalcohol (3A)

A 250 ml flask is charged with 15 g (34.5 mmol, 2.2 eq) of bromide (2)and acetone (100 ml) under an argon atmosphere. To this solution isadded 3,5-dihydroxybenzyl alcohol (2.2 g, 15.7 mmol), 0.82 g (31.0 mmol,0.2 eq) 18-C-6 and 4.77 g (34-5 mmol, 2.2 eq) of K₂CO₃ and the mixtureis stirred for 48 hours whereupon a yellow suspension is formed. To themixture is added methylene chloride (200 ml) and water (200 ml). Theorganic phase is separated, dried over MgSO₄ and evaporated to dryness.A dark brown oil is obtained which is dissolved in toluene (40 ml) andhexane (20 ml). Upon cooling, a white powder forms which is collected byfiltration to give 10.92 g (81.9% of (3A).

3A is converted to the corresponding bromide (3B) by followingsubstantially the same procedure as described above in the formulationof 2.

4. Synthesis of a dendrimer TADDOL

(4R,5R)-2,2-dimethyl-α,α,α′,α′-tetra(4-(3,5-di(4-vinylbenzyloxy)benzyloxy)phenyl)-1,3-dioxolane-4,5-dimethanol(4).

A 50 ml flask is charged with 0.305 g (0.58 mmol) of (1) in acetone 20ml) under an atmosphere of argon. A solution of the bromide (3B) 1.0 g(2.3 mmol, 4 eq) in acetone (5 ml) is added dropwise. To this mixture isadded 0.32 g K₂CO₃ (2.3 mmol, 4 eq). A light yellow suspension thusformed is stirred for 40 hours. Thereafter the mixture is filtered toremove K₂CO₃ and washed with methylene chloride.

The organic phase is collected and the aqueous phase is furtherextracted with methylene chloride (2×100 ml). The organic phases arecombined, dried over MgSO₄ and evaporated to dryness leave a yellow oil(1.2 g) which was further evaporated under vacuum, dissolved inmethylene chloride (100 ml), filtered over Kieselgel, and furtherevaporated to leave a white product (0.72 g) 64.3% of (4).

(4) is a second generation number TADDOL dendrimer. A first generationnumber TADDOL (4A) is formed by following essentially the same procedureas for (4) only substituting bromide (3B) with bromide (2).

5. Copolymerisation of Styrene and dendrimer TADDOL-(4)

The styrene and TADDOL dendrimer (4) are reacted in an 8:1 wt/wt ratio:30 mg of polyvinyl alcohol (PVA) (100,000 Mw, 86-89% hydrolyzed, FLUKA)and water (8 ml) is warmed to 40 to 50° C. and filtered through aG1-glass filter. A 100 ml flask equipped with cooler and stirrer ischarged with the respective amounts of TADDOL dendrimer (4) and styrene,16.4 mg (0.1 mmol) AlBN, 3 ml benzene and 1 ml of THF. The resultant PVAmixture is stirred at room temperature at 750 rpm to form a suspension.The suspension was heated to 90° C. in an oil bath and stirred at 750rpm at this temperature for 40 hours under an argon atmosphere. After 30minutes the suspension is observed to change colour from light yellow towhite. The resultant suspension is cooled to room temperature andfiltered over a G2 glass filter. The filtrate is added to water (200 ml)for washing. Thereafter, the mixture is washed with hot water (75 ml),methanol/water 1:1 (50 ml) and finally pentane (50 ml). After drying athigh vacuum the copolymer is obtained as fine white particles.

EXAMPLE 2 Dendrimer TADDOLate-mediated reaction of diethylzinc andbenzaldehyde

A 50 ml flask is charged with 0.2 mmol of polymer-bound dendrimer TADDOL(4) (0.02 eq) in 10 ml of toluene and 60 μL (0.2 mmol, 0.02 eq) of(i-PrO₄) Ti under argon to form a yellow solution. The mixture isstirred at room temperature for 3 hours before being dried under highvacuum. Thereafter a further 5 ml of toluene is added to the mixture andthe solution cooled to −30° C. To the cooled solution is addedbenzaldehyde (1.0 ml, 10 mmol, 1 eq), 300 μL (1 mmol, 0.1 eq) (i-PrO₄)Ti and diethylzinc (9 ml, 2 M in toluene). After stirring the mixtureat 30° C. for 16 hours NH₄Cl (30 ml) is added and the mixture is warmedto room temperature. The mixture is filtered and washed well withdiethylether. The organic phase is washed with water and collected. Theaqueous washings are further extracted with diethyl ether (2×100 ml) andthe organic phases are combined, dried over MgSO₄ and evaporated todryness to yield a light yellow oil of the addition product.

The polymer-bound TADDOLate dendrimer gave yields of greater than 95%after only 0.5 hours and essentially quantitative yields after only onehour. The addition product was obtained with an enantiomeric ratio (S:R)of 98:2.

When a non-dendrimer polymer-bound TADDOL (a polystyrene polymerattached to the 1:1 diisopropoxytitanium complex of TADDOL(4R,5R)-2,2-dimethyl-α,α,α′,α′-tetraphenyl-1,3-dioxolane-4,5-dimethanol)was employed as the catalyst, the reaction was only 70% complete after 3hours and the addition product was obtained with an enantiomeric ratio(S:R) of 93:7.

What is claimed is:
 1. A composition comprising a polymer bound to orcross-linked to a dendrimer, said dendrimer comprising a member selectedfrom the group consisting of anα,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanol moiety and anα,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanolate of titanium (IV)moiety, said moiety comprising a dendritic substituent, wherein saiddendritic substituent is bound to an α or an α′ aryl group.
 2. Acomposition according to claim 1, wherein said dendritic substituentcomprises a peripheral styryl group.
 3. A composition according to claim2 comprising 8 to 16 peripheral styryl groups.
 4. A particle comprisinga composition according to claim
 1. 5. The particle of claim 4, whereinsaid particle has a size of from about 0.25 to about 0.4 millimeters. 6.A composition comprising a particle according to claim 4 and a pouch,said pouch being comprised of a mesh, said particle being disposedwithin said pouch.
 7. The composition of claim 6 wherein said mesh iscomprised of an inert material.
 8. The composition of claim 7 whereinsaid inert material is polypropylene.
 9. A method for producing adendrimer bound to a polymer, comprising: reacting a polymer or apolymerizable monomer unit of said polymer with a dendrimerα,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanol, wherein said dendrimercomprises an α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanol moiety,said moiety comprising a dendritic substituent, wherein said dendriticsubstituent is bound to an α or an α′ aryl group, and wherein saiddendritic substituent comprises a polymerizable terminal functionalgroup.
 10. A method for producing a dendrimer bound to a polymer,comprising: reacting a titanium-containing reagent with a compositionaccording to claim 1, wherein said composition according to claim 1comprises an α,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanol moiety.11. A method for catalyzing the addition reaction of dialkyl zinccompounds with aldehydes comprising: reacting a dialkyl zinc compoundwith a carbonyl compound in the presence of a composition according toclaim 1, wherein said composition according to claim 1 comprises anα,α,α′,α′-tetraaryl-1,3-dioxolane-4,5-dimethanolate of titanium (IV)moiety.
 12. The method of claim 11 wherein said dialkyl zinc compound isdiethyl zinc.
 13. The method of claim 12 wherein said carbonyl compoundis an aldehyde.